Pesticidal phosphorylated thiourea



highest product yields are United States Patent a $275,502 1 PESTICIDAL PHOSPHORYLATED THIOUREA Glenn R. Price and Edward N. Walsh, Chicago Heights, 111., assignors to Stautfer Chemical Company, New

York, N.Y., a corporation of Delaware No Drawing. Filed June 10, 1964, Ser. No. 374,180 Claims. (Cl. ,167-22} l R10 crnort m ,7

wherein R and R are lower alkyl, X is selected from the group consisting of sulfur and oxygen, R? is hydroxy Patented Sept. 27, 19.66

tion mixture was allowed to stir at room temperaturef o'r sixteen hours and then the water was removed under par tial vacuum. The organic material was separated from the inorganic salts by extraction with acetone. 'I'he acetone was rem'oved and the product concentrated to 50 C. at 1.0 mm. of Hg pressureto yield 96% N-(0,0-dimethylphosporothiono)-N-(hydroxymethyl) N -(ethyl)-N (hy-- droxethyl) thiourea analyzing as 10.4% P and 20.9% S as compared to 10.2% P and 21.1% S theoretical. r

EXAMPLE 2 To 25.6 grams (0.14 mole) of 0,0-dimethylphospho roisothiocyanato thionate in 150 ml. of ether was added 10.5 grams (0.14 mole) of methylaminoethanol at room temperature. The reaction mixture was heated to 70 C.

on a steam cone and then cooled to room temperature and added to 150 ml. of water containing 20.0 grams of potassium carbonate and =ml. of 40% aqueous for- -maldehyde solution. The reaction mixture was allowed to stir for 1-6 hours at room temperature and then the I water was removed under 'alkyl and -R is selected from the group consisting of lower I alkyl and hydroxyalkyl. Suitable lower alkyl radicals for R, R and R include methyl, ethyl, propyl, isopropyl,

'amyl, ootyl, and the like. R and R include such hydroxyethyl, 2-(-hydroxy) 2-(methyl) propyl-ll, 2-(hydPOXY) 2-(methyl) butyl-l, 2-"(hyd'roxy) octyl-1;et'c.. Dhe preferred thioureas of the present invention, namely those The hydroxyalkyl radicals of members are hydroxymethyl,

25- the partial vacuum. The organic material was separated from themor aniesalrs'syex traction with acetone. The acetone was removed and product concentrated, to 50 C. at.,1.0.mm. .of Hg pressure to yield 83% N- (0,0-dimethylphosphorothiono) having the'highest pe'sticidal activity, are those in which either R and/or R contain a hydroxyalkyl with a hydroxyl group in the beta position to the adjacent nitrogen.

The compounds of the present invention may be prepared according to the following general reactions:

wherein R, R R 'R and X are as defined hereinbefore.

and the like. The reaction will proceed at temperatures even as low as 0 C., and the product is stable at fairly high temperatures, at least as high as 100 C. Nevertheless, a preferred temperature range within which the about 20 C. and 50 C.

Although the compounds of the present invention show pesticidal activity generally, their miticidal activity, especially with the two-spotted mite, T etranychus telarius, is unexpectedly high.

The following examples illustrate the principles of the invention and include the best modes presently known for use in practice of these principles. I

EXAMPLE 1 3 )2 2 H) 2 5) (C2H40H),

To a solution of 15.0 grams (0.055 mole) of N*(-O,O,- dimethylphosphorothiono) N -(ethyl)-N -hydroxyethyl) thiourea. was added 8.0 grams (0.06 mole) of potassium traction with acetone. The

P and 20.2% S, theoretical.

usually obtained is between carbonate, ml. of water 'and10 m1. of 40% aqueous j formaldehyde solution at room temperature. The reacrea analyzing as 10.9% P and 22.1% l0.8%-P:-and-22.2% S theoretical.

S as compared to To 25.6 grams (0.14 mole) of -0,0-dimethylphosphor'oisothiocyanato thionate in ml; of ether .was added 14.4 grams (0.14 mole) N-(isopropyl) ethanolamine at room temperature. The reaction'm ixture was heated-to 70 C. on a steam cone, then cooled to room temperature and added to 150 ml. .of water. To thismixture was added 20.0 grams of, potassium carbonate and 25 ml. of 40% aqueous formaldehyde solution. The reaction mixture was allowed to stir for sixteen hours and-then the water was removed under partial vacuum. j The organic material was separated from the inorganic. salts byex.- acetone was removed and the product concentrated to 50 C. at'l.'0. mm. ,ofH'gpressur'e to yield 86% -N-(0,0-dimthylphosphorothiorio)-N-(hydroxymethyl) -N1- (isopropyl) -N (hydro xyethyl) t-hiourea analyzing 10.0% P and 19.8% S as compared' to 9.8%

Using a procedure substantially in accordance with one or more of those described in the foregoing examples, the following specific compounds were prepared.

N-(0,0 diisopropylphosphorothiono)-N(hydroxymeth yl)-N ,N -(d ihydroxyet-hyl) thiourea.-

7 EXAMPLE 6 I 2 5 )2 2 H) 2H4Q s s) N-(0,0 diethylgphosphorothiono)-N(hydroxymethyl).e

N hydroxyethyl)N -(phenyl) thiourea.

Insecticidal activity for thecompounds of the fo rego ing A karnples' is illustrated in Table I wherein the Percentage ill among the pestspecies is reported for a specified uantity o f vcandidate compound, expressed in microrams g-hereintermed'the ,bioassay, test), or for a ercentage concentrationof the compound in aqueous disersion (herein termed the screening test); A slanted ne is used tojseparate the percentage kill for the .test

pecies shown on the left from thepercentage concentra .on or total quantity shown on the right.

' Insect test species lousefly -Muscn domestica Lmerican cockroach-Periplaneta americana ipotted milkweed bug0ncopeltus fasciatus.

.. A Mite lest species- Fwowspotted niite-Tetranychusteldriizs When used hereinthe term pest is intended in the 1' restrictedzsen'se generally recognized in the art as applying to the lower forms of vertebrates, for example, rodents, birds, and larger forms which are"-more commonly controlled by mechanical means such as traps. Itwilllbe apparent to one skilled in the art that the toxic activity. demonstrated hereinbefore TABLE ,I.-"MORTALITY OF REPBESENTATIVE SPECIES -OF COMMON INSECT ORDERS v T.telarius Compound (Exam- M. e 0.

p10 number, see dmn'estica amen'cgmc fizsciatus Syst c p a Post ern- Nymphs Eggs e 7 .bw n

l i-g 50/30 50/01 50 0 .001 100/0 .ooi 50/0 .001 50/0 .001 50/10.; mg 100/01 100/0.1 100 01 100 0005- 100 01 mo/0.1 10 0 11 m p In the screening tests for the insect species'of Table I,

from ten to twenty-five insects were caged in cardboard mailing tubes 3 /8" in diameter and 2 /8" tall. The cages were supplied with cellophane bottoms and screen tops. Food and water were supplied to. each cage. Dispersions of the test compounds were prepared by dissolving one half gram of the toxic material in' 10 ml. of acetone. This solution was then diluted with Water containing 0.0175% was placed ina confined area. The same cageswere employedas for the fly screening test. A weighedamount oftlietoxicant was placed in pyrex petri dishes having a surface area of 18.8 sq. centimetersalong with 1 ml. of acetone. After the solvent was evaporated by air-drying, a cage containing groups of twenty-five female flies, three to five days old, was placed over the residue. Counts of living and dead insects were made forty-eight hours after initiation of the test.

It hasbeen further found that the compounds of the present invention are excellent systemic rniticides. In testingjfor systemic action, pinto bean plants were placed in bottles=containing 200 ml. of the test solution'and were held in place with cotton plugs; Only the roots were immersed. The solutions were prepared by dissolving the candidate miticide in acetone orfother suitable solvent and'then diluting with'tap water. The final acetone con centration of thesolution was never allowed to exceed 1% and the toxicant was initially tested at a concentration of 100 p.p.m. As soon as the .plants were placed in the solution they were infested with mites. Mortalities of post embryonic, nymph and ovicidal forms were determinedsevendays after initiation of the test.

on various test species is indicative of activity with species and orders notspecifically shown. a The foregoing description is given understanding only and no unnecessary limitations should be understood therefrom, as modifications will be obvious to those skilled in the art.

We claim: Y 1. A compound having the formula:

of i" 2*" -P-N.-o-N I R 0 onion B3 wherein R and R are lower-alkyl, Xis selected from the r group consisting of sulfur and oxygen, R? is a hydroxy- 0 alkyl and R is selected from the group consisting of lower-alkyl and hydroxyalkyl.

*2. N-(0,0 dimethylphosphorothiono) N (hydroxy) methyD-N -(ethyl)-N -(hydroxyethyl) thiourea.

3. N-(0,0-dimethylphosphorothiono) N- (hydroxymethyl) -N (isopropyl) -N -(hyd roxyethy1)- thiourea. I 4. N (O,O-dimethylphosphorothiono) N-( hydroxyimethyl)-N-(methyl-Nl(hydroxyethyl) thiourea. 5. A method of contr'ollingpests which comprises contacting said compound having the formula:

R 0 :15no11 1t J Y wherein R and R are lower-alkyl, Xis selected from the group consisting of sulfur and oxygen, R is a hydroxyalkyl, and R? is, selected from the group lower-alkyl and hydroxyalkyls 6. The method of controllingipe'sts which comprises contacting said pests with a pesticidal amount of N-(0,0.- 'dimethy1phosphorothiono) Np- (liydroxymethyl)-,N1-

-(ethyl)-N =(hydroxyethyl) thiourea.

7 life customarily controlled-by chemical means and excludingthe-higher animals, the

for clearness. of

pests with a pesticidal amount of at least one consisting of 7. The method of controlling pests which comprises contacting said pests with a pesticidal amount of N- (0,0- dimethylphosphorothiono) N (hydroxymethyD-N (isopropyl)-N -(hydr0xyethyl) thiourea.

8. The method of controlling pests which comprises contacting said pests with a pesticidal amount of N-(0,0- dimethylphosphorothiono) N (hydr0xymethyl)-N (methyl)-N -(hydroxyethyl) thiourea.

9. A process for preparing a compound of the general formula:

6 alkyl and hydroxyalkyl, which comprises reacting a compound of the formula PNHCN R 0 33 wherein R, R X, R and R are as 'hereinbefore defined, with formaldehyde while maintaining the reaction temperature between about 0 C. and C.

10. The process of claim 9 wherein the reaction is accomplished in the presence of a solvent selected from the group consisting of water, acetone, acetonitrile and ethanol. 7

References Cited by the Examiner UNITED STATES PATENTS 3/1963 Price et al. 167-22 FOREIGN PATENTS 952,712 11/1956 Germany.

JULIAN S. LEVIIT, Primary Examiner. V. C. CLARKE, Assistant Examiner. 

5. A METHOD OF CONTROLLING PESTS WHICH COMPRISES CONTACTING SAID PESTS WITH A PESTICIDAL AMOUNT OF AT LEAST ONE COMPOUND HAVING THE FORMULA: 